CN104785296B - A kind of liquid cobalt sulfonated phthalocyanine catalyst for petroleum gas sweetening - Google Patents
A kind of liquid cobalt sulfonated phthalocyanine catalyst for petroleum gas sweetening Download PDFInfo
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- CN104785296B CN104785296B CN201510117502.7A CN201510117502A CN104785296B CN 104785296 B CN104785296 B CN 104785296B CN 201510117502 A CN201510117502 A CN 201510117502A CN 104785296 B CN104785296 B CN 104785296B
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- phthalocyanine
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- sulfonic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000007788 liquid Substances 0.000 title claims abstract description 41
- -1 cobalt sulfonated phthalocyanine Chemical class 0.000 title claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 21
- 239000010941 cobalt Substances 0.000 title claims abstract description 21
- 239000003209 petroleum derivative Substances 0.000 title claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000003513 alkali Substances 0.000 claims abstract description 25
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- IXROTFPQTYAPMU-UHFFFAOYSA-M [Co]Oc1ccccc1 Chemical compound [Co]Oc1ccccc1 IXROTFPQTYAPMU-UHFFFAOYSA-M 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 19
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 2
- 150000002118 epoxides Chemical class 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- HPAVSHLOCSRBQS-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCCl(C)(C)CC1=CC=CC=C1 Chemical group CCCCCCCCCCCCCCCCCCCl(C)(C)CC1=CC=CC=C1 HPAVSHLOCSRBQS-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 125000005605 benzo group Chemical group 0.000 claims 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 abstract description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 20
- 235000013495 cobalt Nutrition 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000003915 liquefied petroleum gas Substances 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000006277 sulfonation reaction Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KHAZIIVSIJPRGF-UHFFFAOYSA-N [Na].CCCS Chemical compound [Na].CCCS KHAZIIVSIJPRGF-UHFFFAOYSA-N 0.000 description 2
- OEBFEEOMRDUMIR-UHFFFAOYSA-N [S].C(CC)S Chemical compound [S].C(CC)S OEBFEEOMRDUMIR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- QPUSANCBJDDXSA-UHFFFAOYSA-N ethanethiol;sodium Chemical compound [Na].CCS QPUSANCBJDDXSA-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 description 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical group O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a kind of be used for petroleum gas sweetening liquid cobalt sulfonated phthalocyanine catalyst, this liquid catalyst is made up of one of active component four β p-sulfonic acid phenoxyl Cobalt Phthalocyanine, stabilizer Propylene Glycol Dimethyl Ether, N methyl diethanolamine or triethanolamine or compound, emulsifying agent stearyl dimethyl benzyl ammonium chloride and NaOH solution.The invention also discloses the structure of four β p-sulfonic acid phenoxyl Cobalt Phthalocyanines that the present invention designs first, and the catalyzed conversion effect to liquefied gas mercaptan for this liquid catalyst.Catalyst activity component four β p-sulfonic acid phenoxyl Cobalt Phthalocyanine dissolubility in water and alkali liquor of the present invention is fabulous, and has higher removal of mercaptans activity.
Description
Technical field
The invention belongs to PETROLEUM PROCESSING field is and in particular to a kind of liquid cobalt sulfonated phthalocyanine catalyst is in liquid gas sweetening
Application in technique.
Background technology
The harmful components such as mercaptan are contained in liquefied petroleum gas (LPG), because mercaptan has corrosivity, and the gas that gives out a foul smell
Taste, if do not removed, can produce considerable influence to the following process of environment and liquefied gas.At present, LPG removal of mercaptans refines main employing
Merox extracting-liquid phase catalytic oxidation technique or fibrous membrane doctor process.Both technique removes the principle of mercaptan in liquefied gas
Essentially identical, the mercaptan first in liquefied gas, via catalyst-caustic extraction, then will be taken out in the presence of oxygen and catalyst
Sodium mercaptides in extract are converted into disulphide, and alkali liquor and catalyst are regenerated simultaneously, and total chemical equation is：
In above two LPG doctor process, be required for catalyst dissolution in advance in alkali liquor, obtain catalyst-
Alkali liquor.But the solid sulfonated phthalocyanine cobalt being usually used at present or poly- phthalocyanine cobalt catalyst dissolubility in alkali liquor are poor, and impact is urged
Dispersion in alkali liquor for the agent, thus reducing the catalytic conversion efficiency of mercaptan in LPG doctor process, causes the wave of catalyst
Take.
For improving dissolubility in alkali liquor for the metal phthalocyanine catalyst, researcher develops the phthalocyanine of sulfonate or carboxylate
Derivant is as the deodorization catalyst of light petroleum fraction, and the better catalytic activity of cobalt phthalocyanine and vanadyl phthalocyanine.Patent US
4885268 preparation methoies disclosing four sulfonated phthalocyanine cobalts, prepared four sulfonated phthalocyanine cobalts dissolubility in aqueous has
Certain raising, but its catalysis oxidation thiol active is poor relative to two sulfonated phthalocyanine cobalts.Patent US 4248694 disclose single sulfonation,
The mixed liquor of two sulfonation and four sulfonated phthalocyanine cobalts is used as the liquid-liquid deodorization catalyst of light petroleum fraction, and the activity of catalyst has
Improved, but because the low-solubility of single sulfonated phthalocyanine cobalt is so that single sulfonation, two sulfonation and four sulfonated phthalocyanine cobalt mixture are total
Dissolubility is still poor.
Patent US 6740619 discloses the preparation of Cobalt Phthalocyanine and its application in LPG deodorizing technology of sulfanilamide replacement,
With chlorosulfonic acid, the Cobalt Phthalocyanine that the Cobalt Phthalocyanine and ammonia four higher sulfanilamide of water solublity that have been Material synthesis replace, its catalysis activity and
Stability is suitable with industrial catalyst, but raw material chlorosulfonic acid has severe corrosive, dangerous big.
Patent CN 103755713A discloses a kind of preparation method and applications of eight sulfonic phthalocyanin, using macromole
It is easy to isolate and purify, this sulfonation's phthalocyanin metalic has higher water solublity to the method synthesis title complex of salt protection, can be used as
Photosensitizer, photodynamics medicament or photosensitive medicament, but this water-soluble metal phthalocyanine complex structure, preparation cost is high, and fail by
It is used as petroleum fraction desulfuration alcohol catalyst.
At present although existing various metals phthalocyanine derivates are used for the report of petroleum fraction desulfuration alcohol technique, but catalyst
The problems such as generally existing dissolubility difference or activity are high, therefore, the LPG mercaptan-eliminating catalyst of exploitation high activity and highly dissoluble
It is very necessary.
Content of the invention
The problem being existing petroleum gas sweetening catalyst solubility difference to be solved by this invention is it is therefore an objective to provide
A kind of liquid metals sulfonated phthalocyanine catalyst and the application in liquid gas sweetening.This liquid metals sulfonated phthalocyanine coordination compound is urged
Agent and water and alkali liquor have the advantages of good intersolubility, preferable stability, and have higher liquid gas sweetening work
Property.
The present invention adopts the following technical scheme that：
The cobalt sulfonated phthalocyanine coordination compound that the present invention provides, can be named as four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine or 2 (3),
9 (10), 16 (17), 23 (24)-four-(4- sulfonic group -1- phenoxy group) Cobalt Phthalocyanines, its structure is designed first by the present invention, its knot
Structure formula is as follows：
Wherein, substituted radical is in the peripheral position of phthalocyanine ring, referred to as β position, i.e. 2 (3), and 9 (10), 16 (17), 23
(24) position, R represents substituted radicalCoordination compound is named as 2 (3), 9 (10), 16 (17), 23
(24)-four-(4- sulfonic group -1- phenoxy group) Cobalt Phthalocyanines, or referred to as four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine.
Four-β of the present invention-p-sulfonic acid phenoxyl cobaltphthalocyanines can be used as petroleum gas sweetening liquid
The active component of catalyst, has highly-water-soluble and alkali solubility, solves conventional industrial solid sulfonated phthalocyanine cobalt or poly- Cobalt Phthalocyanine
The problem of catalyst solubility difference, and there is excellent removal of mercaptans activity.
Liquid cobalt sulfonated phthalocyanine catalyst of the present invention be used for petroleum gas sweetening method be：
(1) preparation of liquid catalyst：With a small amount of water as solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine, then plus
Enter appropriate 5～15%NaOH solution, add a certain amount of stabilizer and emulsifying agent, shake up so that four-β-p-sulfonic acid phenoxyl
Phthalocyanine cobalt content is 5～25%, stabilizer (one kind of Propylene Glycol Dimethyl Ether, N methyldiethanol amine or triethanolamine or compound)
Content is 0.5～1.5%, and emulsifying agent (stearyl dimethyl benzyl ammonium chloride) content is 0.5%～1%.
(2) liquid catalyst of the present invention as the evaluation methodology of petroleum gas sweetening catalyst is：Liquefaction
The key of oil gas thiols conversion catalyst is the catalytic conversion efficiency to sodium mercaptides, in order to widely evaluate present invention catalysis
The performance of agent, is mixed with appropriate 5～25%NaOH solution with liquid catalyst of the present invention first, controls this catalysis
In agent-alkali liquor mixed liquor, catalyst activity component concentration is 50～200 μ g/g, then in a certain amount of above-mentioned catalyst-alkali liquor
Add the mercaptan sodium solution of dissimilar variable concentrations, 40 DEG C of constant temperature stirrings in mixed liquor, be passed through air and carry out urging of sodium mercaptides
Oxidation, carries out Potential Titration Analysis every sampling in 5 minutes, calculates the removal efficiency of mercaptan sulfur, thus being catalyzed to the present invention
The activity of agent is evaluated.
Or, mixed with appropriate 5～25%NaOH solution with liquid catalyst of the present invention first, control this to urge
In agent-alkali liquor mixed liquor, catalyst activity component concentration is 50～200 μ g/g, then takes a certain amount of above-mentioned catalyst-alkali
Liquid mixed liquor extracts the liquefied petroleum gas containing mercaptan, and agent hydrocarbon ratio is for 1:10～100, extract is the mercaptan containing variable concentrations
Sodium catalyst alkali liquor.This extract stirs in 40 DEG C of constant temperature, is passed through air, carries out catalytic oxidation desulfurization alcohol, samples every 5 minutes
Carry out Potential Titration Analysis, calculate the removal efficiency of mercaptan sulfur, thus with the actual liquefied petroleum gas containing mercaptan to the present invention
The activity of catalyst is evaluated.
Mercaptan removal rate is pressed formula (1) and is calculated：
X%=(C0-C1)×100/C0Formula (1)
In formula：
The removal efficiency of X% mercaptan sulfur；
C0Mercaptan sulphur concentration before catalytic reaction, ppm；
C1Mercaptan sulphur concentration after catalytic reaction, ppm.
The advantage that liquid cobalt sulfonated phthalocyanine composition catalyst of the present invention is used for petroleum gas sweetening is：
(1) sulfonation's phthalocyanin metalic coordination compound active component of the present invention, introduces four p-sulfonic acids on phthalocyanine ring
Phenoxyl, is prepared into tetrasulfonic acid base substituted phthalocyanine, and water solublity, alkali solubility are fabulous, can high degree of dispersion in alkali liquor.
(2) preparation method of liquid catalyst of the present invention is simply it is easy to operate.
(3) liquid catalyst of the present invention has higher removal of mercaptans activity.
Brief description
Fig. 1 is the conversion ratio contrast of two kinds of catalyst removal propanethiol sulfur, a catalyst of the present invention, b industrial solid sulfonation
Phthalocyanine cobalt catalyst.
Specific embodiment
Embodiment 1
Four-β-p-sulfonic acid phenoxyl the cobaltphthalocyanines of the test present invention are respectively in water and 10%NaOH solution
Dissolubility, and contrasted with the dissolubility of the solid sulfonated phthalocyanine cobalt of industrial use at present, result is listed in table 1.
Dissolubility in water and alkali liquor for the table 1 cobalt phthalocyanine of the present invention is simultaneously contrasted with solid sulfonated phthalocyanine cobalt
Application examples 2
With 1mL deionized water as solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.25g, add 10%NaOH molten
Liquid 3.70g, adds 0.025g stabilizer Propylene Glycol Dimethyl Ether, 0.025g emulsifying agent stearyl dimethyl benzyl ammonium chloride, shakes
Even so that four-β-p-sulfonic acid phenoxyl phthalocyanine cobalt content is 5%, stabiliser content is 0.5%, and emulsifier content is
0.5%.Take this liquid catalyst 0.10g to be added in 100g 5%NaOH solution, control in this catalyst-alkali liquor mixed liquor and urge
Agent active component concentration is 50 μ g/g.Take the above-mentioned catalyst solution of 30mL, add micro high concentration ethyl mercaptan sodium solution so that
Mercaptan sulphur concentration about 100 μ g g in reactant liquor-1, 40 DEG C of constant temperature stirrings, it is passed through air, reacts 50 minutes, mercaptan sulfur removal rate is
92.5%.
Application examples 3
With 2mL deionized water as solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.50g, add 5%NaOH molten
Liquid 2.40g, addition 0.050g stabilizer N methyldiethanol amine, 0.050g emulsifying agent stearyl dimethyl benzyl ammonium chloride,
Shake up so that four-β-p-sulfonic acid phenoxyl phthalocyanine cobalt content is 10%, stabiliser content is 1%, emulsifier content is 1%.
Take this liquid catalyst 0.10g to be added in 100g 10%NaOH solution, control catalyst in this catalyst-alkali liquor mixed liquor
Active component concentration is 100 μ g/g.Take the above-mentioned catalyst solution of 30mL, add micro high concentration ethyl mercaptan sodium solution so that anti-
Answer mercaptan sulphur concentration about 120 μ g g in liquid-1, 40 DEG C of constant temperature stirrings, it is passed through air, reacts 50 minutes, mercaptan sulfur removal rate is
95.8%.
Application examples 4
With 3mL deionized water as solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 1.25g, add 15%NaOH molten
Liquid 0.625g, adds 0.075g stabilizer triethanolamine, 0.050g emulsifying agent stearyl dimethyl benzyl ammonium chloride, shakes up,
Four-β-p-sulfonic acid phenoxyl phthalocyanine cobalt content is made to be 25%, stabiliser content is 1.5%, emulsifier content is 1%.Take
This liquid catalyst 0.080g is added in 100g25%NaOH solution, controls catalyst in this catalyst-alkali liquor mixed liquor to live
Property concentration of component be 200 μ g/g.Taking the above-mentioned catalyst solution of 30mL, adding micro high concentration propanethiol sodium solution so that reacting
Mercaptan sulphur concentration about 120 μ g g in liquid-1, 40 DEG C of constant temperature stirrings, it is passed through air, reacts 50 minutes, mercaptan sulfur removal rate is
98.8%.
Application examples 5
With 1mL water as solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.30g, add 12%NaOH solution
2.60g, adds stabilizer triethanolamine 0.025g, Propylene Glycol Dimethyl Ether 0.050g, 0.025g emulsifying agent octadecyldimethyl
Benzyl ammonium chloride, shakes up so that four-β-p-sulfonic acid phenoxyl phthalocyanine cobalt content is 6%, stabilizer total content is 1.5%, breast
Agent content is 0.5%.Take this liquid catalyst 0.200g to be added in 100g 20%NaOH solution, control this catalyst-alkali
In liquid mixed liquor, catalyst activity component concentration is 120 μ g/g.Take the above-mentioned catalyst solution of 30mL, add micro high concentration fourth sulfur
Alcohol sodium solution is so that mercaptan sulphur concentration about 60 μ g g in reactant liquor-1, 40 DEG C of constant temperature stirrings, it is passed through air, react 50 minutes, sulfur
Alcohol sulfur removal rate is 97.0%.
Application examples 6
With 1mL water as solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.30g, add 8%NaOH solution
2.60g, adds stabilizer triethanolamine 0.025g, N methyldiethanol amine 0.050g, 0.025g emulsifying agent hexadecyldimethylamine
Base benzyl ammonium chloride, shakes up so that four-β-p-sulfonic acid phenoxyl phthalocyanine cobalt content is 6%, stabilizer total content is 1.5%,
Emulsifier content is 0.5%.Take this liquid catalyst 0.200g to be added in 100g 20%NaOH solution, control this catalyst-
In alkali liquor mixed liquor, catalyst activity component concentration is 120 μ g/g.Take the above-mentioned catalyst solution of 30mL, add micro high concentration fourth
Mercaptan sodium solution is so that mercaptan sulphur concentration about 60 μ g g in reactant liquor-1, 40 DEG C of constant temperature stirrings, it is passed through air, react 50 minutes,
Mercaptan sulfur removal rate is 97.3%.
Application examples 7
With 1.5mL water as solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.80g, add 5%NaOH solution
2.625g, adds 0.040g stabilizer triethanolamine, 0.035g emulsifying agent stearyl dimethyl benzyl ammonium chloride, shakes up, make
Obtaining four-β-p-sulfonic acid phenoxyl phthalocyanine cobalt content is 16%, and stabiliser content is 0.8%, and emulsifier content is 0.7%.Take
This liquid catalyst 0.100g is added in 100g 15%NaOH solution, controls catalyst in this catalyst-alkali liquor mixed liquor to live
Property concentration of component be 160 μ g/g.Then take a certain amount of above-mentioned catalyst-alkali liquor mixed liquor liquefied petroleum containing mercaptan for the extracting
Gas (mercaptan sulphur concentration about 40 μ g g-1), agent hydrocarbon is than for 1:20, extract is stirred in 40 DEG C of constant temperature, is passed through air, is urged
Change air sweetening, react 50 minutes, mercaptan sulfur removal rate is 96.6%.
Comparison study example
With propanethiol sodium solution (sulfur content about 100 μ g g-1) be model compound, control the present invention prepare catalyst and
Solid cobalt sulfonated phthalocyanine is in equal (cobalt ion concentration about 10 μ in reaction system of the concentration of cobalt ions in reaction system
g·g-1), under the same terms, catalytic reaction, after 50 minutes, contrasts catalyst of the present invention and industrial solid sulfonated phthalocyanine cobalt catalysis
The removal of mercaptans activity of agent, result such as Fig. 1 shows.In figure is the conversion ratio contrast of two kinds of catalyst removal propanethiol sulfur, and a present invention urges
Agent, b industrial solid cobalt sulfonated phthalocyanine.
Catalyst of the present invention is used as LPG mercaptan-eliminating catalyst, has higher catalysis activity, its active and industrial solid
Cobalt sulfonated phthalocyanine is suitable.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.Right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need to be exhaustive to all of embodiment.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (7)
1. one kind is used for petroleum gas sweetening liquid cobalt sulfonated phthalocyanine catalyst, by active component four-β-p-sulfonic acid base benzene
Epoxide Cobalt Phthalocyanine, stabilizer, emulsifying agent and NaOH solution composition.
2. a kind of liquid cobalt sulfonated phthalocyanine catalyst as claimed in claim 1, its active component is to have highly-water-soluble and alkali
The cobalt sulfonated phthalocyanine coordination compound of dissolubility it is characterised in that：It is as follows that the present invention designs its structure first：
Wherein, R represents substituted radicalSubstituted radical is in the peripheral position of phthalocyanine ring, claims
For β position, i.e. 2 (3), 10 (11), 18 (19), 26 (27) positions, it is named as 2 (3), 10 (11), 18 (19), 26 (27)-four-(4- sulphur
Acidic group -1- phenoxy group) Cobalt Phthalocyanine, or referred to as four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine.
3. liquid cobalt sulfonated phthalocyanine catalyst according to claim 1, its stabilizer is Propylene Glycol Dimethyl Ether, N- methyl two
One or more of ethanolamine and triethanolamine.
4. liquid cobalt sulfonated phthalocyanine catalyst according to claim 1, its emulsifying agent is octadecyl dimethyl benzyl chlorine
Change ammonium.
5. according to any one of claim 2-4 liquid cobalt sulfonated phthalocyanine catalyst it is characterised in that the system of liquid catalyst
Preparation Method:With a small amount of water as solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine, add appropriate NaOH solution, plus
Enter a certain amount of stabilizer and emulsifying agent, shake up.
6. liquid cobalt sulfonated phthalocyanine catalyst according to claim 5 it is characterised in that：Four-β in liquid catalyst-right
The mass concentration of sulfonic benzo epoxide Cobalt Phthalocyanine is 5～25%, and stabilizer mass content is 0.5～1.5%, and emulsifying agent quality contains
Measuring as 0.5%～1%, NaOH mass concentration is 5～15%.
7. a kind of application of liquid cobalt sulfonated phthalocyanine catalyst as claimed in claim 1 it is characterised in that：Described liquid cobalt
Sulfonated phthalocyanine catalyst is used for liquid gas sweetening technique.
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| CN108579812B (en) * | 2018-04-18 | 2020-11-06 | 山东澳润化工科技有限公司 | Composite liquefied gas desulfurizing catalyst and its preparing process |
| CN110724150B (en) * | 2019-10-29 | 2021-07-16 | 武汉科林化工集团有限公司 | Preparation method of liquid binuclear cobalt phthalocyanine ammonium sulfonate desulfurization catalyst |
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| GB805562A (en) * | 1956-03-14 | 1958-12-10 | Ici Ltd | New phthalocyanine compounds |
| US4803170A (en) * | 1985-05-09 | 1989-02-07 | Ultra Diagnostics Corporation | Competitive immunoassay method, device and test kit |
| AP9901723A0 (en) * | 1997-06-20 | 1999-12-31 | Univ Carnegie Mellon | Homogeneous oxidation catalysis using metal complexes. |
| JP2002212471A (en) * | 2001-01-17 | 2002-07-31 | Canon Inc | Ink, color filter and its manufacturing method, liquid crystal panel, computer and image display device |
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| EP2436055A1 (en) * | 2009-05-26 | 2012-04-04 | Basf Se | Use of phthalocyanine compounds with aryl or hetaryl substituents in organic solar cells |
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